Complexes of 2-heptadecylimidazolines



metals of. group H of the periodic table.

2,881,179 COMPLEXES OF Z-HEPTADECYLIMIDAZOLINES John N. Hog sett, Charleston, W. Va., assignor to Union Carbide Corporation, a corporation of New York No Drawing. Application March 11, 1957 Serial No. 645,015

9 Claims. (Cl. 260-299) This invention relates to complexes of 2-hepta- 'decylimidazolines and to a process for their preparation. "More particularly, this invention relates to chelates of A specific chelate, which is illustrative of this embodi- I ment of my invention is di(Z-heptadecylimidazoline acetic acid) lead nitrate (C H O N Pb) which can be represented by the structural formula:

HooccH, noooom Di(2-heptadecy1imidazoline acetic acid) lead nitrate (CMHBSOIONflPb) These compositions include the chelates formed by 2,881,179 2 'ig A t 1 3 The compositions of my invention also include the chelates formed by reacting Z-heptadecylimidazoline with the salts of'the metals of group III of the periodic table. Illustrative of such chelates are: triheptadecylimidazoline aluminum sulfate, triheptadecylimidazoline aluminum nitrate and triheptadecylimidazoline aluminum chloride.

My compositions also include chelates formed by re acting acid salts of 2-he'pta'decylimidazoline with the salts of themetals of group III of the. periodic table. Illustrative of such chelates are: tri(heptadecylimidazoline acetic acid) aluminum sulfate, tri(heptadecylimidazoline acetic acid) aluminum nitrate and tri(heptadecylimidazoline acetic acid )v aluminum chloride.

The compositions of my invention also include the chelates formed by reacting Z-heptadecylimidazoline with the salts of the metals of group IV of the periodic table. Illustrative of such chelates are diheptadecylimidazoline lead nitrate and triheptadecylimidazoline tin chloride.

Still other compositions within the scope of my invention are the chelates formed by reacting the acid salts of Z-heptadecylimidazoline with the salts of the metals of group IV of the periodic table. Illustrative of such chelates are di(heptadecylimidazoline acetic acid) lead nitrate and tri(heptadecylimidazoline acetic acid)' tin chloride.

Other compositions within the scope of my invention are the chelates formed by reacting Z-heptadecylimidazo- .line with the salts of the metals'of group VI of the periodic table. Illustrative of such chelates arez. triheptadecylimidazoline chromium sulfate, triheptadecylimidazoline chromium nitrate and triheptadecylimidazo line chromium chloride.

Still other compositions of my invention are the chelates formed by reacting the acid salts of 2-heptadecylimidazoline with the salts of the metals of group VI reacting Z-heptadecylimidazoline with the salts of the metals of group I of the periodic table. Illustrative of such chelates are: diheptadecylimidazoline silver nitrate and diheptadecylimidazoline copper sulfate.

My compositions also include chelates formed by reacting the acid salts of 2-heptadecylimidazoline with the salts of the metals of group I of the periodic table. Illustrative of such chelates are: di(heptadecylimidazo line acetic acid) sodium sulfate, di(heptadecylimidazoline acetic acid) sodium hypophosphate, di(heptadecyl imidazoline acetic acid) silver nitrate, di(heptadecyL imidazoline acetic acid) copper sulfate.

The chelates 'of my invention can also be formed by reacting Z-heptadecylimidazoline with the salts of the Illustrative of such chelates are: diheptadecylimidazoline zinc nitrate,diheptadecylimidazoline zinc chloride, diheptadecylimidazoline cadmium sulfate, diheptadecylimidazoline thev acid salts of Z-heptadecylimidazoline with the salts of the metals of group II of the periodic table. Illustrative of such chelates are: di(heptadecylimidazoline acetic :acid) magnesium sulfate, di(heptadecylimidazoline acetic chloride, di(heptadecylimidazoline I metals of group VIII of the perrodlc table. Illustrative acid) magnesium acetic acid) zinc chloride, di(heptadecylimidazoline acetic acid) cadmium sulfate, di(heptadecylimidazoline acetic acid) cadmium nitrate, di(heptadecylimidazoline acetic acid) mercury sulfate and di(heptadecylimidazoline acetic acid) mercury bromide .t

of the periodic table. Illustrative of such chelates are; tri(heptadecylimidazoline acetic .acid) chromium sulfate, tri(heptadecylimidazoline"acetic acid) chromium nitrate and tri(heptadecylimidazoline acetic acid) chromium chloride I Other compositions within the scope of my invention are the chelates formed by reacting 2-heptadecylimidazoline with the salts of the metals of group VII of the periodic. table. Illustrative of such'chelates are: diheptadecylimidazoline manganese nitrate, diheptadecylimidazo line manganese chloride and diheptadecylimidazoline manganese sulfate.

The compositions of my invention also include chelates formed by reacting the acid salts of Z-heptadecylimidazoline withpthe salts of the metals of groupVII-of the periodic table. Illustrative of such chelates are: di(heptadecylimidazoline acetic acid) manganese nitrate, -di(hepta'- decylimidazoline acetic acid) manganese chloride and di(heptadecylimidazoline acetic acid) ,.manganese sulfate. -Ariother group of compositions within the scope of my invention are the chelates formed by reacting Z-hepta; decylimidazoline with the "salts'of the'metals of group :VIII of the periodic table. Illustrative of such chelates are: triheptadecylimidazoline iron sulfate, triheptadecylimidazoline iron phosphate, triheptadecylimidazoline iron nitrate, triheptadecylimidazoline cobalt sulfate .and die heptadecylimidazoline nickel nitrate.

" Still another group of compositions within the scope of invention are the chelates formed by reacting, the acid'salts'pf 2-heptadecylimidazolinelwith 'the salts of the of such chelates are: tri(heptadecylimidazoline acetic acid) iron sulfate, tri(heptadecylimidazoline.aceticacid) iron phosphate, tri(heptadecylimidazoline acetic acid) iron nitrate, tri(heptadecylimidazoline acetic acid) cobalt 'tri(heptadecylimidazoline) cerium acid sulfate.

Still other compositions within the scope of my invention are the chelates formed by reacting the acid salts of 2-heptadecylimidazoline with the salts of the metals of the lanthanum series of the periodic table. Illustrative of such chelates is tri(heptadecylimidazolineacetic acid) cerium acid sulfate.

The compounds of the present invention can be prepared by a process which comprises bringing a 2-heptadecylimidazoline into reactive admixture with a metal "salt under conditions to'produce a chelate.

The metal salts which are best suited for use in this invention are water-soluble. For this reason, the reaction should be conducted in a solvent medium which comprises at least 80 percent water. Other solvents which can be used together with water are methanol, ethanol, isopropanol and pyridine. The two reactants, namely the 2-heptadecylimidazoline and the metal salt, need not be added to the solvent in any particular order. Preferably, however, in the case of Z-heptadecylimidazoline, the metal salt is dissolved in water and the Z-heptadecylimidazoline is dissolved in an alcohol, such as isopropanol, and the two solutions are combined. In the case of Z-heptadecylimidazoline acetic acid, both reactants are preferably dissolved in water.

The reaction is preferably conducted at 20 to 30 C. but can be conducted at temperatures between about C. and about 80 C.

The following examples are illustrative:

EXAMPLE I Di(Z-heptadecylimidazoline) lead II nitrate to sz s s was prepared as follows:

About 200 grams of anhydrous lead II nitrate were dissolved in 3000 m1. of water and the solution was agitated at a slow rate. To this solution was added 350 ml. of an isopropanol solution containing 90 grams of Z-heptadecylimidazoline. A precipitate formed and was filtered at reduced pressure in a large Buchn'er funnel. The precipitate was washed twice with water and dried. The calculated percentage composition (by weight) for the lead II chelate prepared as described above are compared in Table I. In Table I R is Z-heptadecylimidazoline.

Table I.Percentagecomposition of di(2-heptadecyl- The data obtained agree satisfactorily with the theoretical structure of the lead 11 chelate containing 2 moles of 2+heptadecylimidazolin'e per mole of lead,.in ac'c'ord ancewiththe acceptedcoor'dinant number of 4 for Pb.

EXAMPLE II Tri(2-heptadecylimidazoline) tin H chloride so utoa e a was prepared using the same procedure as in Example 1, except that 175 grams of stannous chloride hydrate (SnCl .2H O) were used in place of the 200 grams of anhydrous lead nitrate. The calculated percent pure compound and the actual composition (by weight) found for the tin II chelate prepared are compared in Table II. In Table II, R is Z-heptadecylimidazoline.

Table II.--Percentage composition of tri(2-hep'ladecylimidazoline) tin II chloride I Calculated,

Percent Found,

Element Composition Percent 3R to 1 Composition The data obtained agree satisfactorily with the theoretical structure of the tin II chelate containing 3 moles of 2-heptadecylimidazoline per mole of tin, in accordance with the accepted coordinant number of 6 for Sn++.

The other chelates of this invention can be prepared in a similar manner.

As disclosed in copending Torgeson application, Serial No. 545,107, filed November 4, 1955, the chelates of this invention are useful as fungicides. Representative chelates contemplated herein were tested for fungicidal activity by means of the slide germination test. Essentially this test method consisted of germinating spores in continual contact, on glass slides, with given concentrations of the chemical under test. The germination was observed after 24 hours and the amount of the chemical needed to inhibit germination of 50 percent (LB. 50 value) of the spores was determined. The procedure used is more fully set forth in a paper entitled The Slide- Germination Method of Evaluating Protectant Fungicides, published in Phytopathology, July 1943, vol. XXXIII, No. 7, pp. 627-632. Two ditferent and typical fungi were used for this test. The fungi tested were Sclerotinz'a fructicola (Winn) Rehm (S.f.) and Alternaria oleracae (A.o.). The values in Table III below represent the parts by weight of the chelate under test, in a million parts by weight of liquid, to prevent the germination of 50 percent of the spores. The liquid used, which of itself did not inhibit germination of the spores, was .Lins solution, which consists of 10 grams of dextrose, 2.46 grams of MgSO -7H O and ml. of distilled water. Ten milliliters of this solution were added to each 100 milliliters of spore.

The periodic table referred to in this application is the periodic table of the elements revised in accordance with the Journal of the American Chemical Society, volume .76, page 2033 (1954).

This application is a continuation-in-part of my pending application, Serial No. 545,108, filed November 4, 1955, now Patent No. 2,789,115.

I claim:

1. A chelate having the structural formula MR,,, wherein R is a member selected from the group consisting of 2-heptadecylimidazoline and acid salts thereof, M is both the anion and cation of an inorganic salt of a metal of group IV of the periodic table and n is an integer having a value of one-half the coordination number of said metal.

2. A chelate having the structural formula MR,,, wherein R is Z-heptadecylimidazoline, M is both the anion and cation of an inorganic salt of a metal of group IV of the periodic table and n is an integer having a value of one-half the coordination number of said metal.

3. A chelate having the structural formula MR,,, wherein R is an acid salt of 2-heptadecylimidazoline, M is both the anion and cation of an inorganic salt of a metal of group IV of the periodic table and n is an integer having a value of one-half the coordination num- 20 her of said metal.

4. A chelate having the structural formula MR wherein R is 2-heptadecylimidazoline acetic acid, M is both the anion and cation of an inorganic salt of a metal of group IV of the periodic table and n is an integer having a value of one-half the coordination number of said metal.

5. A chelate having the structural formula MR wherein R is Z-heptadecylimidazoline acetic acid, M is a tin salt and n is an integer having a value of one-half the coordination number of said metal.

6. Di(Z-heptadecylimidazoline) tin nitrate.

7. Di(2-heptadecylimidazoline acetic acid) tin nitrate.

8. Tri(Z-heptadecylimidazoline) lead chloride.

9. Tri(2-heptadecylimidazoline acetic acid) lead chloride.

References Cited in the file of this patent UNITED STATES PATENTS 2,155,877 Waldmann et a1. Apr. 25, 1939 2,540,171 Kifi Feb. 6, 1951 2,789,115 Hogsett Apr. 16, 1957 FOREIGN PATENTS 531,297 Germany Aug. 7, 1931 OTHER REFERENCES Klingenstein: Ber. Deut. Chem., vol. 28, pp. 1175-76 

1. A CHELATE HAVING THE STRCTURAL FORMULA MRN, WHEREIN R IS A MEMBER SELECTED FROM THE GROUP CONSISTING OF 2-HEPTADECYLIMIDAZOLINE AND ACID SALTS THEREOF M IS BOTH THE ANION AND CATION OF AN INORGANIC SALT OF A METAL OF GROUP IV OF THE PERIODIC TABLE AND N IS AN INTEGER HAVING A VALUE OF ONE-HALF THE COORDINATION NUMBER OD SAID METAL. 